Enhancing the Photoswitching Properties of <i>N</i>-Alkyl Imines

<i>N</i>-Alkyl imines are prevalent in dynamic-covalent chemistry and self-assembled structures, yet their <i>E</i>/<i>Z</i> photochromism is often overlooked due to the high-energy light required for isomerization. Here, we present a simple strategy to enhance their photoswitching properties, achieving switching wavelengths and photostationary state distributions comparable to azobenzene. Moreover, we demonstrate that these <i>N</i>-alkyl imines undergo photoisomerization in the condensed phase and exhibit isomer-dependent fluorescence. We anticipate that this study will inspire the design of photoresponsive architectures that operate directly at the dynamic-covalent bond, eliminating the need for dedicated photoswitchable motifs.